Production of color photographic images



Patented Mar. 16,1954

PRODUCTION OF COLOR PHOTOGRAPHIC IMAGES Jacob Joseph J ennen, Antwerp, Belgium, assignor to Gevaert Photo-Producten N. V., Mortsel, Belgium, a Belgian company N Drawing. Application December 27, 1950, Serial No. 203,023

Claims priority, application Great Britain December 31, 1949 9 Claims.

The present invention relates to a process for the production of color photographic images by color development in the presence of a color coupler, to photographic developers, and photographic material containing such couplers.

As known, a colored image may be formed by developing a reducible silver salt image in the presence of a compound which is referred to as a color coupler and which couples with the oxidation product of the developing agent during the development, forming a dyestuff which is deposited onto the developed silver grains.

My co-pending application Serial No. 66,837, filed December 22, 1948, hereinafter referred to as the co-pending application, discloses compounds which are useable as color couplers for the production of magenta images, said compounds corresponding to the following Formula I wherein Y is a heterocyclic radical; X is alkyl, aryl, acyl or a heterocyclic radical, these groups being either substituted or not, or H; and one or both H atoms of the CH2 groups may be substituted by a substituent split off on development, and which formula may be written in a tautomeric form, for instance, as the following Formula II or, when Y represents a nitrogen-containing heterocyclic ring, a further tautomeric form may be represented by the following Formula III FIG. III

wherein Z is the non-metallic atoms necessary to complete the heterocyclic ring Y; L is a methine group or a substituted methine group; and n is 0 or 1.

0n color development, these color couplers produce dyestufis with an absorption maximum at about 550 ma and an excellent blue-light transmission.

It is an object of the present invention to provide a new process for the production of a colored photographic image by developing a re ducible silver salt image with a primary amino aromatic developing agent in the presence of a color coupler.

It is another object of the present invention to provide a photographic emulsion comprising a color coupler especially suited for the production of magenta images in three-color photographic processes.

Still another object of the present invention is toprovide a photographic color developer comprising a color coupler especially suited for the production of magenta images in three-color photographic processes.

Further objects will appear from the following description.

I have now found that dyestuffs which have a narrow absorption spectrum, as well as dyestuffimages with hard gradation, may be obtained by color development in the presence of compounds wherein the H atom, linked to one of the N atoms in Y, in the 3-amino substituent or in 2-position of the pyrazolone ring, is substituted by alkyl,

aryl, acyl or a heterocyclic group, these substituents being either substituted or not.

According to my present invention, a reducible silver salt image is developed with a primary aromatic amino developing agent in the presence of a color coupler corresponding to Formula, I

FIG. I

X or over said group replacing a hydrogen atom linked to a nitrogen atom.

The preparation of these couplers may be effected by any convenient method, for instance: (a) Acompound corresponding to Formula I or its tautomeric forms is quaternated and treated with alkali during or after'quaternati'ng, e. .g., said compound is treated in alkaline medium with dimethyl sulphate, ethyl bromide, di.-bromo pentane, cetyl bromide or the like.

(1)) A 3-amino-5-pyrazolone is reacted with aheterocyclic compound having a cyclic nitrogen atom quaternated by an'acid residue and a substituent' as define'dabove'and a reactive halogen substituent, i. 'e.,-a halogen atom in'2- or 4-position', for example, 2-iodo-qui'noline ethiodide, 2-bromo-6-methoxy quinoline ethyl bromide (Patent No. 223L659; Example 2), 2-iodo-4- methyl-thiazole-ethiodide (J. Chem. Soc. (1949) 1504-), 2-iodobenzothiazole methiodide (J. Chem. Soc. (1949) 1505), 1-phenyl-3 chloro-5pyrazolone-dimethyl sulphate (Ber. 46(1913) 3694).

(c) A 3-arylor -acyl-amino-5-pyrazolone or a 3-heterocyclic substituted amino pyrazolone according to the cofpending' application is condensed with a heterocyclic compound having a reactive halogen substituent or a reactive mercapto group, as, for example, 2 bromo-pyridine, 2-cliloro-pyridine, Z-chloro-quinoline, 2t4-dichloroquinaz'oline (J. Chem. Soc; (1947) 777), 2'-*bromo-6-methoxy lepidine (J Org; Chem. 457), 6-methoxy-4chloroquinoline (J. Am. Chem. Soc. 69 (1947) 1660), 2-chloro-4-anilino-quinoline (J. Chem. Soc. (1947) 904), cyanuric chloride, 2:4- dichloro-B-anisidino-l13:5 triazine (J. Chem. Soc. (1947) 158), Z-chIoro-thiazole (Chem. Abstracts 40 (-1946) 4-059), 2-chloro-4'z6-dimethylpyrimidine (Ber. 34 (1901) 3956), Z-chlorobenzselenazole (J. Chem. Soc. (-1933) 1765), 1=phenyl-3 chloro-pyrazolone (Ber. 31 (1398) 3008), Q-bromo di benzoxanthene (Beilstein, XVTI, 146) and 4:G-dihydroxy-Z-methylmercapto-pyridine (J. Chem. Soc. (1947) 730).

(d) The thiourea derivative obtained by reacting a 3*-amino5"-pyrazolone with an isothiocyanate is condensed with ethylenebromide, monocliloro acetone or omega-bromo-acetophenone in order-to obtain a thiazoline or a thiazole', or' said derivative is condensed with mono-chloro-acetic acid to obtain a thiazolone.

As 3-amino-5-pyrazolone, any one of those mentioned in the co-pending application may be used as well as their condensation products with an aldehyde, a ketone or the like. Further, 3-amino-5-pyrazolones which may be used are, for instance, the bis-(3-amino-5-pyrazolones) described inPatentNo. 2,411,951.

--color couplers, compounds, such. as 2-ch1om-4- cetyl-amino-quinoline (which may be prepared by a method analogous to that described in the J. Chem. Soc. (1947) 904) are used, the compoundshaving a. substituent' knownto possess the property of rendering them fast to diffusion.

Color couplers which are fast to difiusion may advantageously contain groupings that render them water-soluble. Such groupings may also be introduced into my heterocyclic substituted amino pyrazolones. For instance, a 3-amino-5- pyrazolone-is condensed with the di-primary condensation' product from the reaction of one equivalent of 4:4"-diamino-2:2'-stilbene disulphonic acidand-two equivalents of a heterocyclic compound containing at least two halogen atoms.

Any replaceable. halogen atom still remaining maybe removed'by the reaction with a primary amine (British specification 578,014 and Chem. Abstracts 41 (1947) 6055).

The presence of color couplers according to the present invention during thedevelopment of a reducible silver salt image may result from-adding. to the. photographic material, or to the developer, a compound capable of generating said color coupler, for instance, acompound differing from the-color coupler only in-that one or both of .the hydrogen atoms of the reactive CH2 group or the pyrazolone ring aresubstituted-in-aknown manner by a substituent which splitsbfiduring development.

Example 1- 15 g. 1-phenyl-3-(benzothiazolyl-2-)amino-5- pyrazolone obtained as described in Example 3 of the co-pending application are dissolved in .250 com. of N15 aqueoussolution of NaOH. To

this solution are added 5 com. dimethyl sulfate and the mixture is then heated for 20 minutes on the water bath. After cooling, filtering with suction, and washingthe residue with water and drying, the product obtained is recrystallized from ethanol. The formula is as the following Formula IV FIG. IV

or a derivative of a tautomeric form thereof. Melting point: 199-200? C. Analysis: N calculated 17.39%, found, 17.29% and 17.33%. S calculated 9.98%, found 9.65% and 9.85%.

N,N-diethyl-p-phenylene diamine sulfate g 3.2 .Nazsos g -Water to ccm 500 KzCOs g '75 KBr g 2.5 Water to ccm 500 An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 ccm. water, washed for minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulfate in 1000 ccm. water, and finally washed for 30 minutes. A contrasting magenta image with an absorption maximum at 540 mu is obtained.

Example 2 To g. 1 phenyl 3 phenyl-thiocarbamylamino-5-pyrazolone, melting at 227 C. and obtained as described in Example 3 of the copending application are added 90 com. ethylene bromide. The mixture is boiled for one hour until the greater part of the hydrobromic acid is eliminated. After cooling and filtering with suction, glittering pellets melting at 253-25 C. are obtained. This product is dissolved in an N aqueous solution of NaOH. After treating with acetic acid, the precipitated product is filtered with suction, dried and recrystallized from ethanol. A product of the following Formula V FIG. V

S-CH2 is obtained. Melting point: l97l98 C. Analysis: S calculated 9.52%, found 9.10%.

2 g. of this product are dissolved in 50 com. of an N solution of KOH in alcohol and added to a mixture of solutions as given above in Example 1.

An exposed positive cin film is developed for three minutes at C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 ccm. water, washed for 10 minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulphate in 1000 ccm. water, and finally washed for 30 minutes. A contrasting magenta image with an absorption maximum at 544 mu is obtained.

Example 3 14 g. 1 phenyl-3-pheny1-thiocarbamylamino- 5-pyrazolone and 28 g. mono-chloro acetic acid are melted togethed and heated on the water bath for 30 minutes. The product obtained is recrystallized from ethanol and corresponds to the Formula VI Melting point: 206208 C. Analysis: N calculated 16%, found 15.75% and 15.80%.

2 g. of this product are dissolved in 50 com. ethanol and 25 com. of an N solution of KOH in methanol and added to a mixture of the solutions given in Example 1.

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ierricyanide and 3 g. potassium bromide in 1000 ccm. water. washed for 30 minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulphate in 1000 ccm. water, and finally washed for 30 minutes. A contrasting magenta image with an absorption maximum at 546 m is obtained.

Example 4 26.5 g. 1-phenyl-3-amino-5-pyrazolone, com. pyridine and 24 com. p-tolyl-isothiocyanate are refluxed for one hour. The reaction mixture is cooled to 50 C. and poured into one litre of a 2 N aqueous solution of hydrochloric acid whilst stirring. The precipitate formed is filtered off, washed with water and recrystallized from a mixture of equal parts of ethanol and methanol. Melting point: 257258 C.

6.5 g. of the l-phenyl 3-(toluthiazolyl 2-) amino-5-pyrazolone thus obtained and 30 ccm. acetic acid anhydride areboiled for fifteen minutes. The reaction mixture is poured into water. The precipitated product is separated by filtration with suction and recrystallized from ethanol. It corresponds to the following Formula VII or to a tautomeric form thereof. Melting point; 245-247 C. Analysis: N calculated 15.38%. found 14.90%.

2 g. of this product are dissolved in 40 com. ethanol and 20 com. of an N aqueous solution of KOH and added to a mixture of solutions given in Example 1.

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in. mild-cam; wa er. shedier 1.0 minutes.

iiaedfor-20-m nunisin Math-comp sed o 2.

sodium thiosulphate in 1000 ccm. Water. and finally washed for 30 minutes. A contrasting magenta. image with an absorption maximum at 535 m is obtained;

Examplefi 2 g. of this product are dissolved in 500cm. ethanol and 25 com. of a normal solution of KOH methanol and addedtoa mixture of solutions given inExample 1.

An. exposed positive cin film is developed for threeminutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in. 100.0 com. water, washed for 10 minutes, fixed for 20 minutes in a bath composed of 250 g. sodium. thiosulfate in 10,00 com. water, and finally washed. A contrastin bluish-magenta ima eis obtained.

Example 6 11g. 1 m chloroephenyl-ii-amino--pyrazolone prepared by the method described. in the, J. Am. Chem. Soc. 66 (1944) 1850, 8 com. phenylisothiocyanate and 60 com; pyridine are boiled for 1 hour. The reaction mixture is poured into a 2 N aqueous solution of hydrochloric acid. The hydrochloric acid is decanted and the viscous precipitate is purified by washing with water and suspending in ethanol, After filtration with suction, a product melting at 220-222 C. is obtained.

2.9 g. of this product and 5.8 g. mono-chloro acetic acid are heated on the boiling water bath for half an hour and next boiled with a little ethanol. A product according to the Formula IX :2 oithis enab er a e dissa ved n- .0 c ethanoland 10 com. of a 2. N aquBQussolution-of NaOH a d add d to a mix-tumor thesolutions as indicated in Example 1.

An exposed positive cin film is developed for six minutes at 20 C. in the bath thus obtained. washed for 30 minutes, bleached in order toremove the-silver-in-a bath composed of-50 g. potassium ferricyanide and 3 g. potassium bromidein 1000 ccm. water, washed-for IO-minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulfate in 1000 ccm. water, and finally washed. A magenta image with an absorption maximum at 548 m is obtained.

E am le 7 .7 1 eof h product. obtained as e ribed in Example 7. of the co-pending application and. 1.3 .g. dibromopentane are heated over night ina sealedtubeat 120 C. After cooling, filtering with suction, washing with ether, and recrystallizing from a mixture of equal volumes ethanol and water, a product. corresponding to the following Formula X FIG. X

l S O aNHi A O @NH is obtained. Thisproduct, however, contains an amount of a similar product differing from that of Formula X in that, theQH groups are replaced by chlorine atoms.

2 g. of this productare dissolved in a mixture of the solutions given in Example 1.

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 com. water, washed for 10 minutes, fixed for 20 minutes in a bath composed of 250 g. sodiumthiosulfate in 1000.ccm. water, andfinally washed. A magenta image with, an absorption maximum at 557 me s o ine Example 8..

Raw 1-phenyl-3-amino-5-pyrazolone obtained according to the method described in the J. Am. Chem. Soc. 66 (1944) 1853 is recrystallized from ethanol. The non-dissolved residue is purified by boiling with water and recrystallizing from diethylene glycol mono-ethyl ether. Fine, glitteringpellets melting at 282-285 C. are obtained. It is -3 imino bis (1 phenyl 5 pyrazolone). Analysis: N calculated 21.02%, found 21.31% and 21.36%. On colordevelopment in'thesame manner asexplained hereinafter, this product yields a violet dye image.

10 g. of this product are gradually added to 21 g. sulfuric acid. Next, 4 g. chloro-sulfonic acid are. added. The-mixture-is lowly h a d up to 1119 andsubseguently maintainedat -4 9" 6. to three hours Th reaction mixtu e i poured into ice-water under stirring. After filtration with suction and recrystallization from II I N 50 OaNa or to a tautomeric form thereof is obtained.

2 g. of this product are dissolved in a mixture of the solutions given in Example 1.

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 ccm. water, Washed for minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulfate in 1000 ccm. water, and finally washed for 30 minutes. A magenta image is obtained.

Example 9 5.25 g. 1-pheny1-3-amino-5-pyrazolone, 3.4 g. chloropyridine and com. glacial acetic acid are slightly boiled for 4 hours. After adding 2 g. sodium acetate, the reaction mixture is poured into water. After filtering with suction and boiling with ethanol, the residue not dissolved melts at 280 C. and i a product which corresponds to the following Formula XJI FIG. XII

2 g. of this product are dissolved in 50 ccm. ethanol and 10 com. of an N aqueous solution of NaOH and added to a mixture of the solution given in Example 1.

An exposed positive cine film is developed for three minutes at C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50 g. Do-

tassium ferricyanide and 3 g. potassium bromide in 1000 ccm. water, washed for 10 minutes, fixed for 20 minutes in a bath composed of 250 g. so-

dium thiosulfate in ccm. water, and finally washed. A bluish magenta image is obtained.

Example 10 cipitate is filtered with suction. The product ob- V tained is alpha-(3-aminc-5-pyrazo1onyl-1) oenanthic acid.

3 g. of this product and 2 g. 2-chloro-benzoxazole are melted together at C. for 10 minutes. After cooling, 2. product which is alpha- 3-(benzoxazolyl-2) amino-5-pyrazolonyl-l oenanthic acid is obtained.

2 g. of this product dissolved in 6 com. of a 2 N aqueous solution of NaCI-I and 0.5 ccm. dimethyl sulfate are heated for half an hour on the water bath. The reaction mixture is cooled and poured into a 0.1 N aqueous solution of acetic acid. The precipitate formed is filtered with suction, washed with water, and dried in the air. A product corresponding to the following Formula XIII FIG. XIII or to a tautomeric form thereof is obtained.

1 g. of this product is dissolved in 10 com. ethanol and added to 100 com. of a positive cinematographic silver halide emulsion. The emulsion is coated to a support, exposed to light, developed for three minutes at 20 C. in a bath obtained by mixing the solutions given in Example 1, washed for 30 minutes, bleached in order to remove the silver in a bath'composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 ccm. water, washed for 10 minutes, fixed for 20 minutes in a bath composed of 250 g. sodium thiosulfate in 1000 ccm. water, and finally washed for 30 minutes. A magenta image is obtained.

Example 11 3 g. 3-anilido-5-pyrazolone prepared according to the method described in J. Am. Chem. Soc. 65 (1943) 733 and 3 g. 2-chloro-benzthiazole are melted together at C. A vigorous reaction occurs. When this reaction comes to an end, the whole is cooled, and as much of the reaction mixture as possible is dissolved in boiling ethanol. The solution is filtered. By adding ether, about 1 g. of a product is precipitated which is recrystallized from 100 com. of a mixture 01 1 part by volume of water and 3 parts of ethanol. The product obtained corresponds to the following Formula XIV Melting point 165-170 C. Analysis: N calculated 15.87%. found 16.35%.

2 g. of this product are dissolved in 50 com. ethanol and ccm. of an N aqueous solution of NaOH and added to a mixture. of the solutions as. given in Example 1.

An exposed positive cin, film is developed for three minutes at C. in the bath thus. obtained, washed for minutes, bleached in order to remove the silver in a bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide 1000 cam. water, washed for 10. minutes, fixed for 20 minutes in a bath composed of 250 g. sodium, thiosulfate in 1000 com. water, and finally washed for 3.0 minutes. A bluish magenta image is obtained.

Example. 12

1 g. 1-phenyl-3- (benzthiazolyl-2 -amino-5- pyrazolone and 0.5 g. 2-amino-benzthiazole are melted together at, 180 C. for one hour according to the method described for the preparation of 2-imino-B-(benzthiazolyl-2') -benzthiazoline in Ber. '75 (1942) 9-46. A product corresponding to the following Formula XV FIG. XV

is obtained.

2'. g. of, thisv product are dissolved in 40 com. methanol and added to av mixture of the solutions given in Example 1..

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus, ob.- tained, washed for 30 minutes, bleached in order to remove the silver ina bath composed of 50 g. potassium ferricyanide and 3 g. potassium bromide in 1000 com. water, washed for 150 minutes, fixed for 20 minutesin a bath com-posedof 250 g. sodium thiosulfate in 1000 com. water, and finally washed for- 30 minutes. A magenta image is obtained.

Example 1 5 g; of the raw beta-Ebeta benzthiazolyl 2- hydrazinoli-beta-imino-propionic acid ethyl ester prepared according to the method described in- J. Am. Chem. Soc. 66 (1-944) 1854 are dissolved in amylacetate. 0.5 g; of the product does not dissolve. It melts above 300 C. and is 3-im-ino- 12 bls'E1- -(benzthiazolyl-2 -5-pyrazolone] Analysis'f N' calculated 21.92%, found 22.18%.

0 .4 g. of this product suspended in 3- com-.- of an N aqueous solution of NaOI-I and 0.1 com. dimethylsulfate are heated on the boiling water bath for 30 minutes. The reaction mixture is cooled. The precipitate obtained is filtered with suction. A product corresponding to the following Formula XVI is obtained. Melting point above 300 C.

1 g. is dissolved in 10 com. ethanol and 10 com. of an N aqueous solution of NaOH and added to a mixture of the solutions of Example 1.

An exposed positive cin film is developed for three minutes at 20 C. in the bath thus obtained, washed for 30 minutes, bleached in order to remove the silver in a bath composed of 50- g. potassium ferricy-anide and 3 g. potassium bromide in 1000 com. water, washed for 10 minutes, fixed for 20 minutes a bath composed of 250 g. sodium thi'osulfate in- 1000 ccm. water, arid finally washed for 30 minutes. A magenta image is obtained.-

Example 14 3 g. I-phenyl-3-phenylthiocarbamyl-amino-5- pyifazolone melting at 227 C. and prepared as described in' Example 3 of the co-pending application, 2 g. omega bromo-acetophenone and 510' com. ethanol are boiledfor 45 minutes. After cooling and filtering with suction, the filtrate is neutralized with a 2N aqueous solution of N'aQI-I. After filtration. with suction, a product melting; at, 116-118; C. is obtained.

4.1 g of this product, 3.1 g. beiizalldehyde-ZA- disod-ium sulfonate. and 30 com. water containin 0.1. g. of NaQH are heated. on the water bath for about 1 hour., From the, yellowishbro.wn reaction mixture obtained, a. dye is precipitated common salt. This product corresponds to the following Formula FIG. XVII fixed for 20 minutes in a bath composed of 250 g. sodium thiosulfate in- 1 000- water, and

finally washedfor so minutes A nice mgenta image is: obtained.-

2. A color photographic developer containing a primary amino aromatic developing agent and a color coupler according to the formula COCHI 3. A color photographic developer containing a primary amino aromatic developing agent and a color coupler according to the formula CH3 4. A color photographic developer containing a primary amino aromatic developing agent and a color coupler according to the formula o it 5. A light-sensitive color photographic material containing a silver halide emulsion layer and a colloid layer comprising a color coupler having the formula 6. Process for the production of a color photographic image, which comprises developing a reducible silver salt image in a photographic element by means of a primary amino aromatic developing agent in the presence of a color coupler having a formula selected from the group consisting of the following three formulae:

lit

wherein Y is a heterocyclic radical, X is a member selected from the group consisting of alkyl, aryl, acyl, a heterocyclic radical, and hydrogen, R is a member selected from the group consisting of alkyl, aryl, acyl, and a heterocyclic group, Z is the non-metallic atoms necessary to complete a heterocyclic radical, the heterocyclic radical in the definitions of Y, X, R and Z being a radical selected from the group consisting of 5 and G-membered heterocyclic radicals containing at least one nitrogen atom and of such radicals having a fused-on ring, n is a value selected from the group consisting of 0 and 1, and L and L are methine groups.

'7. Process for the production of a color photographic image, which comprises developing a reducible silver salt image in a photographic element by means of a primary amino aromatic developing agent in the presence of a color coupler having a formula selected from the group consisting of the following three formulae:

wherein X is a member selected from the group consisting of alkyl, aryl, acyl, a heterocyclic radical, and hydrogen, R is a member selected from the group consisting of alkyl, aryl, acyl, and a heterocyclic group, Z is the non-metallic atoms necessary to complete a heterocyclic radical, the heterocyclic radical in the definitions of X, R and Z being a radical selected from the group consisting of 5 and G-membered heterocyclic radicals containing at least one nitrogen atom and of such radicals having a fused-on ring, n is a value selected from the group consisting of 0 to l, and L and L' are methine groups.

8. A light-sensitive photographic material comprising a silver halide emulsion layer and a colloid layer. containing a color coupler having a amatewherein Y is a heterocyclic -radical,"X is a member selected from the group consisting of alkyl, aryl, acyl, a heterocyclic radical, and hydrogen, R is a member selected from the group consisting of alkyl, aryl, acyl and a heterocyclic group, Z is the non-metallic atoms necessary to complete aheterocyolic:radical, the heterocyclic radical in the definition of. It and Z bein s radica selec ed om the g ou cons t g of handmembered heterocyclic, radicals containing v at leastonenitrogenatom. and-of suchradicals hiavr ng a iused-onfrin enisa :value .se1ec dir m th emueconsi ne Qf-0 and .-1, land-L nd L are methi e groups.

9. A color photographic developer containing a mimary amino arom ic. de eloping ag n -and alcolor coupler having, zaiormula sele t dpfrom. thezgmup consistmg;'ofythefo l wns three .iQr-. mulae:

wherein Y is a heterooyclic radical, X is a member selected from the group consisting of alkyl, aryl, cxlha he e szy w i al and hydr en, eRis a,-member selected fromflthe group consisting of alkyl, ry ci nd a et o y lic g ou Z is the non-metallic atoms necessary to com-' plete a heterocyelic radical, the heterocyclic radical in the definitions of Y, X, R. and Z being a radical selected from the group consisting of 5 and G-memberedheterocyelic radicals containing at least one nitrogen atom and of such radicals having a fused-0n ring, 1 is a value selected form the group consisting of 0 and l, and L and L are methine groups.

JACOB JOSEPH JENNEN.

References Cited in the file of this patent ITED VSTATESU TTENTS Number Name Date 2,311,081 Porter et a1. Feb. 16, 1943 2,343,703 Porter et al. Mar. '7, 1944 FOREIGN PATENTS Number Country Date 558,855 GreattBritain Jan. 25, 1944 

6. PROCESS FOR THE PRODUCTION OF A COLOR PHOTOGRAPHIC IMAGE, WHICH COMPRISES DEVELOPING A REDUCIBLE SILVER SALT IMAGE IN A PHOTOGRAPHIC ELEMENT BY MEANS OF A PRIMARY AMINO AROMATIC DEVELOPING AGENT IN THE PRESENCE OF A COLOR COUPLER HAVING A FORMULA SELECTED FROM THE GROUP CONSISTING OF THE FOLLOWING THREE FORMULAE: 